O Chem Extra Material Alkene Alkyne Rxns Halogenation and EAS Electrophilic Addition to Alkenes Reagents What s added HBr or HCl HI H and BrH3O H and OHH ROH H and ORBr2 CCl4 or Cl2 Br and BrBr2 H2O Br and OHCl2 H2O Cl and OHBr2 ROH Br and ORCl2 ROH Cl and OR 1 Hg OAc 2 H2O H and OH 2 NaBH4 1 Hg OAc 2 ROH H and OR 2 NaBH4 1 BH3 THF H and OH 2 H2O2 OH H2O H2 catalyst H and H Catalyst Pt C Pd C or Ni HBr ROOR peroxide H and Br 1 RCO3H OH and OH 2 H3O 1 OsO4 OH and OH 2 H2O2 KMnO4 cold dilute OH OH and OH Alkynes Reduction Addition of Hydrogen H2 Regioselectivity Markovnikov Markovnikov Markovnikov Markovnikov Stereose lectivity Anti Anti Intermediate carbocation carbocation carbocation bromonium ion bromonium ion Rearrange ments Possible Possible Possible Not possible Not possible Markovnikov Anti bromonium ion Not possible Markovnikov Anti Not possible Markovnikov Anti mercurinium ion mercurinium ion AntiMarkovnikov Syn Not possible Syn Not possible AntiMarkovnikov Anti Not possible Syn Not possible Syn Not possible radical Not possible Not possible H2 Pd C Pd C H2 Lindlar s catalyst Na NH3 l Addition of H2O H2SO4 OH tautomerization O OH O Terminal alkynes require HgSO4 as a catalyst Markovnikov O HgSO4 tautomerization H2SO4 OH Hydroboration oxidation with a terminal alkyne produces an aldehyde anti Markovnikov HO H 1 Sia BH THF tautomerization 2 2 H2O2 OH H2O O Nucleophilic Addition of Acetylide Ions NaNH2 C A strong nucleophile An acetylide ion has 3 typical electrophiles 1 an alkyl halide Br C 2 a carbonyl C O Br 3 an epoxide adds to least substituted side C O O OH H3O Organometallic Reactions Formed by combining an alkyl halide with Li or Mg R X 2Li R Li LiX R X Mg ether R MgX 1 an allylic or benzylic halide Br MgBr MgBr2 2 a carbonyl C O MgBr O H3O MgBr O 3 an epoxide adds to the least substituted side O MgBr O MgBr Oxidative Cleavage of Alkenes Reducing conditions B 1 O3 78 C 2 Zn H2O or CH3 2S Oxidizing conditions A KMnO4 hot concentrated OH or with H3O 2 H2O2 B 1 O3 HO H3O OH Mg OH Br Aromatic Compounds Criteria for Aromatic Compounds 1 cyclic and containing conjugated pi bonds 2 each atom in the ring must have an unhybridized p orbital 3 planar structure 4 delocalization of the pi electrons must lower the electronic energy 4N 2 electrons Antiaromatic compounds satisfy the first 3 rules above but delocalization of the pi electrons increases the electronic energy 4N electrons Nonaromatic compounds are those that don t satisfy one or more of the first 3 rules above Side Chain Reactions of Benzenes Permanganate Oxidation O 1 KMnO4 OH boil 2 H3O OH HO Chromic acid Na2Cr2O7 H2SO4 achieves the same reaction O Side chain Reduction Clemmenson Reduction reduces ketones and aldehydes to alkanes O Zn Hg HCl H2O Wolff Kishner Reduction does the same thing with H2NNH2 OH heat Electrophilic Aromatic Substitution C E E E E H H H C C E Activating Ortho Para Directors Deactivating Meta Directors